Process for curing resins by mixing therewith a curing amount of an amide of a halo-substituted dicarboxylic acid



United States Patent Oflice 3,391,112 Patented July 2, 1968 3,391,112 PROCESS FOR CURING RESINS BY MIXING THEREWHTH A CURING AMOUNT OF AN AMIDE 01? A HALO-SUBSTiTUTED DlCAR- BOXYLIC ACID Charles M. Hayes, Hoffman Estates, 111., assignor to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 329,950, Dec. 12, 1963. This application Dec. 6, 1965, Ser. No. 512,011

Claims. (Cl. 260-47) ABSTRACT OF THE DISCLOSURE Curing of epoxy resins and polyurethane resins at about 100-150 C. with imides of polyhalopolyhydromethanonaphthalenedicarboxylic acids.

This application is a continuation-in-part of my copending application Ser. No. 329,950, filed Dec. 12, 1963, now Patent No. 3,280,143, Oct. 18, 1966.

This invention relates to a process for the treatment of certain resinous materials utilizing the condensation product of a halo-substituted polyhydropolycyclicdicarboxylic acid or anhydride thereof and an amine compound. More particularly, the present invention is concerned with a process for treating certain resinous materials with certain compositions of matter hereinafter set forth in greater detail to effect a change in the physical characteristics of said resinous materials.

It has now been discovered that some polymeric compositions of a type hereinafter set forth in greater detail may be treated with a composition of matter comprising the condensation product of a particular type of halosubstituted polyhydropolycyclicdicarboxylic acid and anhydride thereof and a primary amine compound to form resins or plastics which will possess certain desirable characteristics. These compounds which are utilized to treat the polymeric compositions of matter will be referred to in the present specification and appended claims as imides of polyhalopolyhydromethanonaphthalenedicarboxylic acids. The imides, when added to these polymeric compositions of matter and specifically resins which are referred to as epoxy resins or polyurethane resins, will act as curing agents or chain extenders therefore and impart useful properties to the treated resins. For example, an epoxy resin or a polyurethane resin which has been cured or chain extended and cured, by the addition of an imide which has been prepared according to a process hereinafter described in greater detail, will be fire resistant or flame retardant, the resin being self-extinguishing when removed from the direct action of the flame. This property of being fire resistant or flame retardant will be especially useful when preparing articles of commerce such as architectural paneling, acoustical sound deadeners in walls, ceilings, etc., or other articles of commerce which are used in places Where the danger of fire is present.

In addition, it is also contemplated that the imide of the polyhalopolyhydromethanonaphthalenedicarboxylic acid may be used as one of the materials in an interfacial polymerization process which is useful in imparting shrink-proofing properties to fibrous materials, and particularly to wool. The interfac-ial polymerization process is effected by treating the fibrous material with an imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid and thereafter further treating the fibrous material with a polyacid polyhalide containing at least two acid halide groups per molecule, both the imide and polyacid polyhalide being in solutions which are mutually immiscible with one another. The formation of the polymer on the fibrous material and particularly wool will impart a shrink-proofing property to the material as well as many other desirable physical characteristics including smoothness after drying, excellent hand, increased break strength and tear strength as well as improved resistance to abrasion, chemicals and pilling. The use of the imides in the present invention as one of the reactants in forming the polymer is advantageous inasmuch as the fibrous material, and particularly wool, after treatment thereof will no have the desirable characteristics of the fibrous material altered nor will a post-cure of the material be necessary. Due to the particular configuration of the imide of the polyhalopolyhydromethanonaphthalenedicarbox ylic acid, the fibrous material will also possess antibacterial, antifungal and insecticidal properties.

It is therefore an object of this invention to provide a process for the treatment of various materials utilizing an imide of a polyhalopolyhyd-romethanonaphthalenedicarboxylic acid to impart desirable characteristics to said material.

A further object of this invention is to provide a process for curing certain resinous materials utilizing an imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid, said process imparting certain desirable physical characteristics to said resins.

In one aspect, an embodiment of this invention resides in a process for the treatment of a resinous material which comprises admixing said resinous material with an imide of a polyhalopoiyhydromethanonaphthalenedicarboxylic acid, thereafter treating the resultant mixture at an elevated temperature, and recovering the treated resinous material.

A specific embodiment of this invention is found in a process for the treatment of an epoxy resin which comprises treating said epoxy rsein with N-(aminoethylaminoethyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide at a temperature in the range of from about ambient to about 150 C., thereafter treating the resultant mixture at a temperature in the range of from about 100 to about 150 C., and recovering the treated epoxy resin.

Other objects and embodiments will be found in the following further detailed description of this invention.

The polyhalopolyhydromethanonaphthalenedicarboxylic acids or anhydrides thereof which comprise one of the starting materials utilized in the present process may be prepared in any suitable manner such as the Diels-Alder reaction of a conjugated aliphatic diene with an olefinic dicarboxylic acid or anhydride. Examples of conjugated aliphatic dienes which may be used include 1,3-butadiene, Z-methyl-1,3-pentadiene, 1,3-pentadiene, etc.; olefinic dicarboxylic acids or anhydrides which may be used include maleic acid, maleic anhydride, fumaric acid, etc. The Diels-Alder condensation will take place at an elevated temperature in the range of from about to about 250 C. or more and at a pressure sufficient to maintain a major portion of the reactants in a liquid phase, said pressure being in a range of from about atmospheric to about atmospheres or more. The tetrahydrophthalic acid or anhydride thereof which results from the aforementioned condensation is then further condensed with a conjugated halo cycloalkadiene to form the desired product, examples of said halo-substituted cycloalkadiene including tetrachlorocyclopentadiene, hexachlorocyclopentadiene, tetrabromocyclohexadiene, hexabromocyclopentadiene, etc. The second condensation reaction is also effected at elevated temperatures in a range of from about 50 C. to about 250 C. or more and at pressures ranging from atmospheric up to about 100 atmospheres or more, the pressure again beingsuificient so as to maintain a major 3 portion of the reactants in the liquid phase at the reaction temperature.

Examples of polyhalopolyhydromethanonaphthalenedicarboxylic acids or anhydrides thereof which may be utilized as a starting material in the present process include 5,6,7,8,9,9 hexachloro l,2,3,4,5,5a,8,8a-octahydro- 5,8-rnethano 2,3 naphthalenedicarboxylic acid, 5,6,7,8, 9,9-hexachloro 1,2,3,4,5,5a,8,Sa-octahydro-S,S-methano- 2,3 naphthalenedicarboxylic anhydride, 5,6,7,8,9,9hexabromo-1,2,3,4,5,5a,8,8a octahydro 5,8 methano-2,3- naphthalenedicarboxylic acid 5,6,7,8,9,9-hexabrm0-l,2,3, 4,5,5a,8,8a-octahydro-5,8-methano 2,3 naphthalenedicarboxylic anhydride etc.

Examples of amine compounds which may be utilized in the process of the present invention as the other starting materials to thus form the desired compositions of matter utilizable in the present invention will possess the generic formula:

in which R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylamine, alkylenepolyamine, polyaikylenepolyamine, arylamine, arylenepolyamine, polyarylenepolyamine, cycloalkylamine, cycloalkylenepolyamine, and polycycloalkylenepolyamine radicals. Specific examples of these compounds which must contain at least one primary nitrogen atom include alkylmonoamines such as methylamine, ethylamine, propylamine, butylamine, the isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl amines, etc.; amines prepared from fatty acid derivatives such as tallow amine, hydrogenated tallow amine, lauryl amine, stearyl amine, oleyl amine, linoleyl amine, etc.; alkylene polyamines such as ethylenediamine, propylenediamine (diamino propane), butylenediamine, pentylenediamine, hexylenediamine, etc., N-alkyl substituted diamino alkanes such as N-methyldiaminoethane, N-ethyldiaminoethane, N-methyl-1,3-diaminopropane, N- ethyl-1,3-diaminopropane, other N-alkyl-l,3-diaminopropanes in which the alkyl group may contain carbon atoms ranging from 2 up to about carbon atoms and thus the alkyl group is selected from hexyl, heptyl, octyl, nonadecyl, undecyl, dodecyl, tridecyl, tetradecyl, etc. radicals. In addition, other N-alkyl diaminoalkanes such as the N- alkyl 1,4 diaminobutanes, N-alkyl-1,2-diaminopentanes, N-alkyl 1,5 diaminopentanes, N-alkyl-1,2-diaminohexanes, N-alkyl-1,3-diaminohexanes, N alkyl 1,6-diaminohexanes, etc., may also be used.

Other amine compounds which may be used include polyalkylenepolyamines and N substituted derivatives thereof including diethylenetriamine, dipropylenetriamine, dibutylenet-riamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, etc., triethylenetetramine, tripropylenetetramine, tributylenetetramine, tripentylenetetramine, trihexylenetetramine, triheptylenetetramine, trioctylenetetramine, etc., tetraethylenepentamine, tetrapropylenepentamine, tetrapentylenepentamine, tetrahexylenepentamine, tetraheptylenepentamine, etc., pentaethylenehexamine, pentapropylenehexamine, pentabutylenehexamine, pentapentahexamine, etc.

It is also contemplated within the scope of this invention that N-alkyl-l,3-diaminopropanes in which the alkyl group contains from about 8 to about carbon atoms of which a number of the class are commercially available may also be utilized although not necessarily with equivalent results. For example, certain amine compounds known as Duomeen T and Diam 26 in which the alkyl group is derived from tallow and contains from about 12 to about 20 carbon atoms per group and mostly 16 to 18 carbon atoms per group may be utilized as the amine starting material in the present invention.

Aromatic amines which may be used include monoamines such as aniline, the toluidines, the xylidines, naphthylamine, anthracylamine, etc.; aromatic polyamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,2 naphthalenediamine, 1,4 naphthalenediamine, 1,5 naphthalenediamine, 1,6 naphthalenediamine, 1,7 naphthalenediamine, 1,8 naphthalenediamine, 2,3 naphthalenediamine, 2,6 naphthalenediamine, 2,7 naphthalenediamine, 1,2,3 triarninobenzene, 1,2,4 t-riaminobenzene, 1,3,5 triaminobenzene, etc., polyarylenepolyarnines such as diaminodiphenylamine, diaminodinaphthylamine, aminodinaphthylamine, etc.; cycloalkylamines such as cyclobutylamine, cyclopentamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, o-methylcyclobutylamine, m-methylcyclo- P butylamine, p-methylcyclobutylamine, m-cyclopentylamine, p-methylcyclopentylamine, o-methylcyclohexylamine, p-methylcyclohexylamine, etc., cycloalkyleneamines such as the isomeric cyclobutyldiamines, cyclopentyldiamines, cyclohexyldiamines, cycloheptyldiamines, cyclooctyldiamines, etc., polyalkylenepolycycloalkylenepolyamines such as diaminodicyclobutylamine, diaminodicyclopentylamine, diaminodicyclohexylamine, the tricycloalkyltetramines, the tetracycloalkylpentarnines, etc.

It is to be understood that the aforementioned amine compounds are only representatives of the class of compounds falling within the generic formula hereinbefore set forth, and that the present invention is not necessarily limited thereto.

The desired compositions of matter which are used in the process of the present invention may be prepared by condensing a polyhalopolyhydromethanonaphthalenedicarboxylic acid or anhydride thereof of the type hereinbefore set forth in greater detail with an amine compound containing at least one primary nitrogen atom at condensation conditions and preferably in the presence of a substantially iner-t organic solvent including aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, etc.; or cyclic parafiins such as cyclopentane, cyclohexane, methylcyolopentane, etc. The reaction is preferably effected at elevated temperatures in the range of from about to about 250 C. or more, the particular reaction temperatures being dependent upon the solvent which is utilized in the reaction, the reaction usual- 1y being effected at the reflux temperature of the solvent. In addition, the reaction time will be dependent to some extent upon the particular temperature which is employed and will usually range from about one-half up to about 5 hours or more.

The process in which the desired compositions of matter which are to be used in the process of the present invention are prepared may be effected in any suitable manner and may comprise either a batch or continuous type operation. When a batch type operation is used, an amine compound of the type hereinbefore set forth in greater detail is placed in an appropriate reaction vessel along with, if so desired, a substantially inert organic solvent such as benzene, toluene, etc. The polyhalopolyhydromethanonapht'halenedicarboxylic acid or anhydride thereof is slowly added thereto, the reaction usually being exothermic. To control this exothermicity, the amine compound may be cooled prior to the addition of the acid or an-hydride and the rise in temperature controlled by utilization of any external cooling means such as an ice bath. Upon completion of the addition of the acid or anhydride the reaction mixture is heated to the reflux temperature of the solvent, if one is used, or to a predetermined reaction temperature which may be in the range of from about 50 to about 250 C. or more. The reaction vessel which is utilized for the process of the invention is provided with means for removing the water which is formed during the reaction. Upon completion of the desired residence time which, as hereinbefo-re set forth, may range from about one-half up to about 5 hours .or more, which is evidenced by the removal of the theoretical amount of water, the reaction mixture is allowed to cool to room temperature. Following this, the solvent may be removed by distillation followed by removal of the excess amine compound. In this respect it should be noted that the amine compound is usually present in the original reaction mixture in a ratio of from about 1.5 up to about moles of amine per mole of acid or anhydride.

The reaction product is recovered and purified by conventional means such as washing with water, dissolving in alcohol and drying. The purified product is then recovered.

It is also contemplated within the scope of this invention that the desired compositions of matter comprising imides of a polyhalopolyhydromethanonaphthalenedicarboxylic acid may be prepared in a continuous manner of operation although not necessarily with equivalent results. When such a method is used, the quantity of the starting materials comprising the polyhalopolyhydromethanonaphthalenedicarboxylic acid or anhydride thereof and an excess of the amine compound along with an organic solvent are continuously charged to a reaction vessel which is maintained at the proper operating conditions of temperature or pressure. Upon completion of the desired residence time in the reaction vessel, the reactor efiluent is continuously removed. The unreacted starting materials are separated from the efiiuent and recycled to form a portion of the feed stock. The remainder of the effluent is then further subjected to fractional distillation to remove the solvent and water and thereafter purified and recovered by conventional means.

The compositions of matter which 'are utilized for the treatment of resinous material according to the process of this invention possess the generic forumla:

in which R is selected from the group consisting of hydrogen, alkyl and alkylamine of from 1 to about carbon atoms, alkylenepolyamine and polyalkylenepolyamine having from 2 to 8 carbon atoms in each alkylene radical, aryl, arylamine, arylenepolyamine and polyarylenepolyamine of from about 1 to 3 carbocyclic rings and cycloalkyl, cyc-lo'alkylamine, cycloalkylenepolyamine and polycycloalkylenepolyamine having from 4 to 8 carbon atoms in the ring, and X is selected from the group consisting of hydrogen and halogen radicals, at least two Xs being halogen, the preferred halogen atoms being chlorine and bromine.

Some specific examples of the imides of polyhalopolyhydromemethanonaphthalenedicarboxylic acids which fall within the generic formula hereinbefore set forth include N (aminoethylaminoethyl)-5,6,7,8,9,9 hexachloro 1,2, 3,4,5,5a,8,8a octahydro 5,8 methano 2,3-naphthalene dicarboxylic acid imide which may also be designated as the diethylenediamino imide of 5,6,7,8,9,9- hexachloro l,2,3,4,5,5a,8,8a octahydro 5,8-methano- 2,3 naphthalenedicarboxylic acid, N (aminopropylaminopropyl) 5,6,7,8,9,9 hexachloro l,2,3,4,5,5a, 8,8a octahydro 5,8 methano- 2,3 naphthalenedicarboxylic acid imide also designated as the dipropylenediamino imide of 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a, 8,8a octahydro 5,8 -methano 2,3 naphthalenedicarboxylic acid, N (aminobutylaminobutyl) 5,6,7, 8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano 2,3 naphthalenedicarhoxylic acid imide also designated as the dibutylenediamino imide of 5,6,7,8,9,9- hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8 methano- 2,3 naphthalenedicarboxylic acid, N (aminoethyl)-5, 6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro5,

8-methano 2,3 naphthalenedicarboxylic acid imide also designated as the ethyleneamino imide of 5,6,7,8,9,9- hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8-methano- 2,3 naphthalenedicarboxylic acid, N (amino-n-butyD- 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro- 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the n butyleneamino imide of..5,6, 7,8,9,9 hexachloro l,2,3,4,5,5a,8,8a octahydro-5,8- methano 2,3 naphthalenedicarboxylic acid, N-(aminot-butyl) 5,6,7,8,9,9 hexachloro 1,2,3,-4,5,5a,8,8a-octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the t butyleneamino imide of 5,6,7,8,9,9 heXachlor-o 1,2,3,4,5,5a,8l,8a octahydro- 5,8 methano 2,3 naphthalene dicarboxylic acid, N- (aminophenyl) 5,6,7,8,9,9 hexachloro l,2,3,4,5,5a, 8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the phenyleneamino imide of 5, 6,7,8,9,9 hexachloro 1,2,3,4,5,5a, 8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid, N (aminophenylaminophenyl) 5,6,7, 8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano 2,3 naphthalenedicarboxylic acid imide also designated as the diphenylenediamino imide of 5,6,7,8, 9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano 2,3 naphthalenedicarboxylic acid, N (aminotolyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a-octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the tolylamino imide of 5, 6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro-5, 8 methano 2,3 naphthalenedicarboxylic acid, N- (aminotolylaminotolyl) 5,6,7,8,9,9 hexachlor0-1,2,3, 4,5,5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the ditolyldiamino imide of 5,6,7,8,9,9 hexachloro 1,2,3,4,5, 5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid, N (aminocyclohexyl) 5,6,7,8,9,9- hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8-methano- 2,3 naphthalenedicarboxylic acid imide also designated as the cyclohexyleneamino imide of 5,6,7,8,9,9 hexachloro l,2,3,4,5,5a,8,8a octahydro 5,8 methano-2, 3 naphthalenedicarboxylic acid, N (aminocyclohexylaminocyclohexyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,5, 5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid imide also designated as the dicyclohexylenediamino imide of 5,'6,7,8,9,9 hexachloro-1,2, 3,4,5,5a,8,8a octahydro 5,8 methano 2,3-naphthalenedicarboxylic acid, N (aminocyclopentyl) 5,6,7,8, 9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano 2,3 naphthalenedicarboxylic: acid imide also designated as the cyclopenteneamino imide of 5,6,7,8,9, 9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano 2,3 naphthalenedicarboxylic acid, N-(aminopentylaminopentylaminopentyl) 5,6,7,8,9,9 hexachloro- 1,2,3,4,5,5a,8,8a octahydro 5,8 methano 2,3-naphthalenedicarboxylic acid imide also designated as the tripentenetriamino imide of 5,6,7,8,9,9 hexachloro-1,2,3, 4,5,5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid, the corresponding N alkylated, cycloalkylated and arylated imides of 5,6,7,8,9,9 hexabromo 1,2,3,4,5,5a,8,8a octahydro 5,8 methano-2,3- naphthalenedicarboxylic acid, etc. It is to be understood that the aforementioned compounds are only representative of the class of compounds which may be prepared and that the present invention is not necessarily limited thereto.

As hereinbefore set forth, it has now been discovered that the imides of the polyhalopolyhydromethanonaphthalenedicarboxylic acids which have been prepared according to the process hereinbefore described may be utilized as additives for certain polymeric compositions of matter and particularly resinous materials. The imides may be used as additives with epoxy resins or polyurethane resins whereby the final product will possess advantageous physical properties, one of which is high degrees of flame retardancy. The epoxy resins in an uncured state are usually thermoplastic and may range from low viscosity liquids to high melting point brittle solids. One example of an epoxy resin which may be cured by the addition of the imides of the present invention is the condensation product of epichlorohydrin and bisphenol-A. The polyurethane resins will comprise polyethers or polyesters which contain OH terminals which are admixed with a polyisocyanate such as, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenol diisocyanate, triphenylmethane triisocyanate, etc., to form polyurethane intermediates which may then be foamed by the addition of a foaming agent, said foaming agent being capable of liberating gaseous products when warmed or reacted with the isocyanate. Examples of foaming agents which may be used include water, acids such as formic acid; polymethylol phenols, trichlorofluoromethane, etc. The resins may be treated by admixing an imide of an acid of the type hereinbefore set forth with a resin and thereafter treating the mixture by treatment at an elevated temperaure in the range of from about 100 to about 150 C. for a predetermined period of time. The resultant product will have the physical characteristics thereof altered to their desirable values and thus may be utilized for various purposes such as floor surfacings, coating, acoustical coatings, sound deadeners, etc. Among these desirable characteristics is the excellent flame retardancy as well as the color stability of the finished product, said finished product retaining a transparency without discoloration as compared to other epoxy resins or polyurethane resins which do not contain the imide of the type hereinbefore set forth in greater detail. In addition, it is also contemplated within the scope of this invention that other compounds which possess fire retardant properties such as antimony and phosphorus compounds may be added to the mixture during the curing of the resin.

As hereinbefore set forth, the resins, both epoxy resins or polyurethane resins are cured or chain extended and cured by treating said resins with an imide of a polyhalohydromethanonaphthalenedicarboxylic acid. The treating is effected at a temperature in the range hereinbefore set forth by admixing the resin and the imide at a temperature in the range of from ambient temperature (about 25 C.) to about 100 C. until the mixture becomes homogeneous. Thereafter, the mixture is poured into molds of the desired shape and in addition, if so desired, may contain a mold releasing agent which will facilitate removal of the treated resin from the mold. The mold is then heated to the desired temperature by external heating means and the treatment of the resin is effected during a period ranging fro-m about 1 hour to about hours or more. Upon completion of the treating step the resin is removed from the mold and utilized as such or cut into desired shapes and sizes.

The following examples are given to illustrate the process of the present invention which, however, are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

Example I One method of preparing the desired compositions of matter which are used in the process of the present invention is shown by the following example in which 258 g. (2.5 moles) of diethylenetriamine was placed in a reaction vessel provided with a water trap. During a period of 1 hour, 213 g. (0.5 mole) of 5,6,7,8,9,9-hexachloro-l,2,3,4,5,5a,8,8a octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride was gradually added thereto. Following this, 200 cc. of benzene was added, the reaction mixture was heated and maintained at reflux temperature (about 85 C.) for a period of about 1.5 hours. During this time approximately 9 cc. of water was removed during the refluxing. The benzene was then removed by distillation on a steam bath and the excess diethylenetriamine was removed by distillation under high vacuum. After removal of the solvent and excess amine the reaction mixture was a yellow-orange brittle solid having a basic nitrogen equivalent weight of 220 g. The product was ground to a fine powder, washed several times with water, dissolved in methyl alcohol and dried using anhydrous sodium sulfate. The mixture was then filtered and the methyl alcohol was evaporated. This left a red viscous clear liquid which crystallized to a red solid upon standing. The product had a basic nitrogen equivalent weight of 262 g. which corresponds to a theoretical nitrogen equivalent of 255 for the equal mole reaction product comprising N-(aminoethylaminoethyl)- 5,6,7,8,9,9-hexachloro l,2,3,4,5,5a,8,8a octahydro5,8- methano-2,3-naphthalenedicarboxylic acid imide also designated as the diethylenediamino imide of 5,6,7,8,9,9- hexachloro-1,2,3,4,5,5a,8,8a octahydro-S,8-methano-2,3- naphthalenedicarboxylic acid.

Example II To illustrate another method of obtaining the compositions of matter which are used to cure resins according to the process of the present invention, 206 g. (2.0 moles) of diethylenetriamine was charged to a reaction flask provided with a Dean-Stark adapter stirring and heating means. The flask was immersed in an ice bath until the temperature of the diethylenetriamine was lowered to about 3 C. Following this, g. (0.2 mole) of 5,6,7,- 8,9,9hexachloro 1,2,3,4,5,5a,8,8a octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride was slowly added during a period of 15 minutes. The immediate reaction upon the addition of the anhydride was exothermic, the well temperature reaching 15 C. The reaction mixture was then allowed to Warm to room temperature and thereafter heated for three hours at a temperature of about 180 C. At room temperature the reaction mixture was an amber viscous slurry containing undissolved material. During the heating period all of the material dissolved. The reaction was considered complete when 4 cc. of water had been collected in the adapter. The solution was then allowed to cool to room temperature and the desired product comprising N-(aminoethylaminoethyl)-5,6,7,8,9,9-hexachloro 1,2,3,4,5,5a,8,8a octahydro- 5,8-methano-2,3-naphthalencdicarboxylic acid imide was recovered.

Example III In this example, 38 g. (0.2 mole) of tetraethylenepentamine, 42.6 g. (0.1 mole) of 5,6,7,8,9,9-hexachloro-1,2,- 3,4,5,5a,8,8a-octahydro-5,8 methano 2,3-naphthalenedicarboxylic anhydride and cc. of benzene was placed in a reaction flask of a similar nature to those hereinabove described. The reaction mixture was heated to reflux temperature (about 83 C.) and maintained thereat for a period of about 4 hours. During this time all of the theoretical water was recovered in the adapter. The flask and contents thereof were allowed to cool to room temperature, the benzene removed and the excess tetraethylenepentamine was removed, the desired product comprising N (aminoethylaminoethylaminoethylaminoethyl)-5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid imide also designated as the tetraethylenetetramino imide of 5,6,7,8,9,9-hexachloro 1,2,3,4,5,5a,8,8a octahydro-5,8- methano-2,3-naphthalenedicarboxylic acid being recov ered.

The above experiment was repeated using 189 g. (1.0 mole) of tetraethylenepentamine and 42 g. of the anhydride. However in this experiment the amine compound and anhydride were reacted in the absence of any solvent, the reaction being effected by heating the mixture to a temperature of about 200 C. for a period of about 2 hours. At the end of this time the flask and contents thereof were cooled to room temperature, excess tctraethylenepentamine was removed by distillation and the product recovered.

9 Example IV In this example 60 g. (1.0 mole) of ethylene-diamine are placed in a reaction vessel which is thereafter cooled to a temperature of about 10 C. by immersing the flask in-an ice bath. To the cooled amine is added 42.6 g. (0.1 mole) of 5,6,7,8,9,9-hexachloro-1,2,3,4,5,Sa,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride during a period of about minutes. The temperature of the flask will rise due to the exothermicity of the reaction and upon completion of the addition of the why dride the flask and contents thereof are allowed to warm to room temperature. Following this, 100 cc. of benzene are added and the flask and contents thereof are then heated to a temperature of about 85 C. and maintained thereat for a period of about 4 hours, the reaction being completed when the theoretical amount of water which is formed during the reaction is recovered in the water trap. At the end of this time the flask and contents thereof are allowed to cool to room temperature. The solvent is removed by distillation on a steam bath and the excess amine is removed by distillation under high vacuum. The desired product comprising N-(aminoethyl)-5,6,7,8,9,9- hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8 methano- 2,3-naphthalenedicarboxylic acid imide also designated as the ethyleneamino imide of 5,6,7,8,9,9-hexachloro-l,2,3,4, 5,5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid is recovered.

Example V In this example, 200 g. (1.0 mole) of diaminodiphenylamine is dissolved in toluene and the mixture is placed in a reaction flask which is thereafter maintained at room temperature by external means. 85 g. (0.2 mole) of 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro- S,8-methano 2,3-naphthalenedicarboxylic anhydride is slowly added to the mixture during a period of about 15 minutes. Upon completion of the addition which is accompanied by a rise in temperature due to the exothermic nature of the reaction, the flask meanwhile being maintained at approximately room temperature, the reaction mixture is heated to the reflux temperature (about 115 C.) and maintained thereat for a period of about 4 hours during which time the theoretical amount of water formed during the reaction is collected in a water trap. Upon completion of the reaction, the flask and contents thereof are allowed to cool to room temperature, the toluene is removed by distillation as is the excess diarninodiphenylamine and the desired product comprising N- (aminophenylarninophenyl) 5,6,7,8,9,9-hexachloro 1,2, 3,4,5,5a,8,8a octahydro 5,8 methano 2,3-naphtha enedicarboxylic acid imide also designated as the diphenyldiamino imide of 5,6,7,8,9,9-hexachloro-1,2,3,4,5, 5a,8,8a octahydro 5,8 methano 2,3 naphthalenedecarboxylic acid is recovered by conventional means.

Example VI In this example, the mixture of 123 g. (1.0 mole) of 1,2,4-triaminobenzene and 150 cc. of benzene is placed in a reaction flask of a nature similar to that utilized in the above examples. Following this, 85 g. (0.2 *mole) of 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro- 5,8-rnethano-2,3-naphthalenedicarboxylic anhydride is gradually added thereto during a period of about 15 minutes. The flask is then heated to a temperature of about 85 C. and maintained thereat for a period of about 4 hours during which time the theoretical amount of water formed during the reaction is removed. At the .end of this time the flask and contents thereof are cooled to room temperature following which the solvent and excess amine compound are removed in a manner similar to that hereinbefore set forth. The desired product comprising N (diaminophenyl) 5,6,7,8,9,9 hexachlor0 1,2,3,4,5,5a,8,8a octahydro 5,8 methano 2,3- naphthalenedicarboxylic acid imide also designated as the phenyldiamino imide of 5,6,7,8,9,9-hexachloro-1,2,3,

10 4,5,5a,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylic acid is recovered by conventional means.

Example VII This example illustrates the use of an imide of 5,6,7, 8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano-2,3-naphthalenedicarboxylic acid as a curing agent for resinous materials. A liquid epoxy resin having an epoxide equivalent weight of 190 and known in the trade as Epon 828 was used as the resin. A mixture comprising 170 g. of N-(aminoethylaminoethyl)-5,6,7, 8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8- methano-2,3-naphthalenedicarboxylic acid imide and 190 g. of epoxy resin was warmed on a steam bath. After several minutes the mixture became homogenous and was poured into molds which had been prepared from glass sheets and Teflon spacers. In addition, a mold release agent was also used to facilitate removal. The molds were placed in an air circulating oven and the curing of the resin took place at C. for a period of about 6 hours. By utilizing various widths of spacers, A2 and A" sheets of resin were prepared. The sheets were cut into ,42 and 1" strips which were used for evaluation of the resin. It was found that the epoxy resin which had been cured by the addition of N-(aminoethylaminoethyl)- 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro- 5,8-methan0-2,3-naphthalenedicarboxylic acid imide had the following properties:

Heat Distortion Temperature (ASTM D648) p. s. i.

at 85 C 264 Hardness (Shore Durometer, Type D) 89 In addition to the aforementioned properties of the cured epoxy resin, the resin, due to the presence of the particular imide, was self-extinguishing when removed from the direct action of a flame.

Example VIII In this example N-(aminoethylaminoethylaminoethylaminoethyl) 5,6,7,8,9,9 hexachloro-ll,2,3,4,5,5a,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylic acid imide which was prepared according to the process set forth in Example III is used to cure an epoxy resin. A mixture of 190 g. of a liquid epoxy resin having an epoxide equivalent weight of 190 and known in the trade as Epon 828 and g. of N-(aminoethylaminoethylaminoethylaminoethyl) 5,6,7,8,9,9-hexachloro-1,2,3,4,5, 5a,8,8a octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid imide is warmed on a steam bath. When the mixture has become homogeneous it is poured into molds which are prepared from glass sheets and Teflon spacers. The resin is cured in an air circulating oven at a temperature of about 100 C. for a period of 6 hours. The sheets which have been cured are removed and tested in a manner similar to that set forth in Example VII above, the strips showing similar properties of heat distortion and hardness as well as being selfextinguishing when removed from the direct action of a flame.

Example IX In this example a mixture of 138 g. of N-(aminoethyl) 5,6,7,8,9,9 hexachloro-1,2,3,4,5,5a,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid imide and 190 g. of a liquid epoxy resin is warmed in a steam bath and after the mixture has become homogeneous, it is poured into molds of a similar nature to that set forth in Examples VII and VIII. The mixture is cured in an air circulating oven at a temperature of C. for a period of 6 hours. At the end of this time the sheets of resin which have been prepared are cut into strips and subg'ected to physical property evaluation. The physical properties of this resin are similar in nature to that found in the above examples as to heat distortion and hardness and in addition the strip of resin is self-extinguishing when removed from a direct action of a flame.

1 1 Example X A mixture of about 130 g. of N-(aminophenylaminophenyl) 5,6,7,8,9,9-hexachloro-1,2,3,4,5,5a,8,8a-octahy- 'dro-5,8-methano-2,3-naphthalenedicarboxylic acid imide In this example, a mixture of 138 g. of N-(diaminophenyl)'5,6,7,8,9,9-hexachloro l,2,3,4,5,5a,8,8a-octahydro-5,8-methano-2,3,-naphthalenedicarboxylic acid imide and 190 g. of a liquid epoxy resin is warmed in a steam bath and after becoming homogeneous is poured into molds of a similar nature to those used in Example VII above. The mixture is thereafter cured at a temperature of about 100 C. for a period of about 6 hours and the resulting cured resin is subjected to physical property evaluation. The resin will be found to be self-extinguishing when removed from the direct action of a flame and Will, in addition, possess excellent heat distortion and hardness properties.

Example XII In this example, a liquid isocyanate terminated prepolymer is prepared by admixing hexamethylene diisocyanate and polypropylene glycol in the usual manner. The prepolymer thus formed is dissolved in methyl ethyl ketone in such an amount so that there is prepolymer and 80% ketone present in the solution. Following this, N (aminoethylaminoethyl)-5,6,7,8,9,9-hexachloro-1,2,3, 4,5,5a,8,8a octahydro 5,8-methano-2,3-naphthalenedicarboxylic acid imide is also dissolved in methyl ethyl ketone. The two solutions are thereafter admixed in such a proportion so that the imide is present in the final mixture in an amount of about 10% by weight of the total solution. After the solution has become homogeneous it is cast on glass and the methyl ethyl ketone solution is allowed to evaporate. The admixture is then placed in an air circulating Oven and the curing of the polyurethane resin is effected at a temperature of 100 C. for a period of about 2 hours. At the end of this time, the resin is recovered and will be found to possess flame retardant properties as well as being stable to light for an extended period of time.

I claim as my invention:

1. A process for curing epoxy resins having a plurality of 1,2-epoxy groups and polyurethane resins having a plurality of free isocyanate groups, which comprises admixing with the resin a curing amount of an imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid, thereafter heating the resultant mixture at a curing tem perature, and recovering the cured resin.

2. The process as set forth in claim 1, further characterized in that said admixing is effected at a temperature in the range of from ambient to about 150 C. and said heating is effected at a temperature in the range of from about to about C.

3. The process as set forth in claim 1, further characterized in that said resin comprises an epoxy resin condensation product of epichlorohydrin and bisphenol A.

4. The process as set forth in claim 1, further characterized in that said resin comprises a polyurethane having free isocyanate groups.

5. The process as set forth in claim 1, further characterized in that said imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid comprises N-(aminoethylaminoethyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8aoctahydro 5,8-methano-2,3-naphthalenedicarboxylic acid imide.

6. The process as set forth in claim 1, further characterized in that said imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid comprises N-(aminoethyl)- 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a-octahydro-5,8- methane-2,3-naphthalenedicarboxylic acid imide.

7. The process as set forth in claim 1, further charac terized in that said imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid comprises N-(aminophenylaminophenyl) 5,6,7,8,9,9 hexachloro-1,2,3,4,5,5a,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylic acid imide.

8. The process as set forth in claim 1, further characterized in that said imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid comprises N-(diaminophenyl)-5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a-octahydro- 5,8-methano-2,3-naphthalenedicarboxylic acid imide.

9. The process as set forth in claim 1, further characterized in that said imide of a polyhalopolyhydromethanonaphthalenedicarboxylic acid comprises N-(aminoethylaminoethylaminoethylaminoethyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,5,5a,8,8a octahydro 5,8 methane-2,3- naphthalenedicarboxylic acid imide.

10. The process of claim 4 further characterized in that said polyurethane is the reaction product of a polyisocyanate and a polyether of polyester containing OH terminals.

References Cited Lee et al., Epoxy Resins, p. 15 relied on, McGraw- Hill Co., Inc., New York, 1957.

WILLIAM H. SHORT, Primary Examiner.

T. D. KERWIN, Assistant Examiner. 

